Lubricant



Patented June 6, 1939 UNITED STATES T OFFHQE Hammond, Ind.,

assignors to Standard Oil Company, Chicago, 111., a corporation of Indiana No Drawing. Application June 10, 1937, Serial No. 147,483

20 Claims.

This invention relates to lubricants and, in particular, to addition agents imparting to lubricants improved properties.

Our invention has particular utility in preventing and/or inhibiting the corrosion of hard metal alloy bearings such as copper-lead, cadmium-nickel, and cadmium-silver bearings which, to a large extent, have replaced soft metal bearings such as Babbitt metal in the trend toward internal combustion engines having high compression ratios and having increased acceleration and 1 increased speed characteristics. The use of the hard metal bearings has created lubricating and corrosion problems, particularly in connection with highly refined oils, some of which may be very corrosive to the hard metal bearmgs.

By highly refined lubricating oils we mean viscous oils which have a minimum viscosity in 0 the range of S. A. E. 10 oils and which have been subjected to such refining processes such as, for example, solvent extraction, that the paraffinicity of the oil is markedly increased. It has been found that highly refined lubricating oils cause corrosion to alloy bearings of the cadmium-silver type to the extent of 5 mg/cm and even greater when such bearings are submerged for 25 hours or less in an air agitated oil which has been preoxidized at about 340 F. for 25 to 50 hours. The

motor oils may be highly refined lubricating oils as such or mixtures of highly refined lubricating oils with less highly refined lubricating oils, or stated in another way, mixtures of corrosive oils and non-corrosive oils, examples of the latter being lubricating oil fractions from Winkler crude or crudes of the Winkler type.

We have found that corrosion to hard metal alloy bearings of the cadmium-silver type by highly refined mineral lubricating oils can be inhibited by adding to such oils a small amount, up to 2% but preferably 0.25% to 0.75% of an organic ester of selenic acid selected from the group consisting of selenic acid esters having the general formula OSe(X R); and Oble(X R) chlorselenate, phenyl chlorselenate, butyl phenyl selenate,v phenyl propyl selenate, dodecyl chlorselenate, propyl chlorselenate, dichlorbutyl selenate, dibutyl thioselenate, diphenyl thioselenate, chlorphenyl chlorselenate.

To determine the effectiveness of the organic esters of selenic acid in inhibiting corrosion to hard metal alloy bearings of the cadmium-silver type in the presence of corrosive mineral lubricating oils, the same are tested by submerging test strips of cadmium-silver alloy in an oil corrosive to such materials in the absence of an inhibitor, and another set of the same alloy test strips are submerged in the oil to which is added 0.25% of an inhibitor and the oils maintained at a temperature of about 341 F. while passing 10 liters of air per hour through the oils. The test strips are removed periodically and weighed and the time required for the strips to lose 5 mgs./sq. cm. of surface noted. With dibutyl selenate as the corrosion inhibitor the following results were obtained:

Time for 5 mgs. loss per sq. mi. of surface Oil Less than I (lay.

The above data clearly indicate the effectiveness of the organic esters of selenic acid in inhibiting corrosion to hard metal alloys of the cadmiumsilver type in the presence of corrosive mineral lubricating oils.

We have also discovered that the hereinbefore described compounds effectively reduce engine wear.

While we have described our invention with a specific embodiment thereof, it is to be understood that the same is merely illustrative of the invention and not a limitation thereof, except insofar as the same is defined in the appended claims.

Weclaim:

1. A motor oil non-corrosive to hard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting of cadmium-silver alloys, cadmium-nickel alloys and copper-lead alloys containing an organic ester of selenic acid selected from the group consisting of selenic acid esters having the general formula OSe(XR.)2 and 0Se(X R) in which R is a radical selected from the group consisting of alkyl, aryl, hydro aryl, aralkylchloralkyl and chloraryl, Y is a halogen and X is an element selected from the group consisting of oxygen and sulfur, said organic ester of selenic acid being added in an amount not greater than about 2% but sufficient to render said motor oil non-corrosive to said hard metal alloys.

'2. A motor oil non-corrosive to hard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting of cadmium-silver alloys, cadmium-nickel alloys and copper-lead alloys containing an organic ester of selenic acid having the general formula OSe(OR)2 in which R is a radical selected from the group consisting of alkyl, aryl, hydro aryl, aralkyl, chloralkyl and chloraryl, said organic ester of selenic acid being added in an amount not greater than about 2% but sufficient to render said motor oil non-corrosive to said hard metal alloys.

3. A motor oil non-corrosive to hard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting of cadmiumsilver alloys, cadmium-nickel alloys and copperlead alloys containing an organic ester of selenic acid having the general formula 0 Se(OR) in which R is a radical selected from the group consisting of alkyl, aryl, hydroaryl, aralkyl, chloralkyl and chloraryl and Y is a halogen, said organic ester of selenic acid being added in an amount not greater than about 2% but suificient to render said motor oil non-corrosive to said hard metal alloys.

4. A motor oil non-corrosive to hard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting of cadmium- 'silver alloys, cadmium-nickel alloys and copperlead alloys containing not more than about 2% of a dialkyl selenate but in amounts suflicient to render said motor oil non-corrosive to said hard metal alloys.

5. A motor oil non-corrosive to hard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting of cadmiumsilver alloys, cadmium-nickel alloys'and copperlead alloys containing not more than about 2% of a diaryl selenate but in amounts sumcient to render said motor oil non-corrosive to said hard metal alloys.

6. A motor oil non-corrosive tohard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting of cadmiumsilver alloys, cadmium-nickel alloys and copper lead alloys containing not more than about 2% of dibutyl selenate but in amounts suflicient to render said motor oil non-corrosive to said hard metal alloys.

7. A motor oil non-corrosive to hard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting of cadmiumsilver alloys, cadmium-nickel alloys and copperlead alloys containing an organic ester of selenic acid having the general formula OSe(SR')z in which R is a radical selected from the group consisting of alkyl, aryl, hydroaryl, aralkyl, chloralkyl and chloraryl, said organic ester of selenic acid being added in an amount not greater than about 2% but suflicient to render said motor oil non-corrosive to said hard metal alloys.

8. A mineral lubricating oil non-corrosive to hard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting aic eai of cadmium-silver, cadmium-nickel and copperlead alloys which comprises a highly refined mineral lubricating oil normally corrosive to hard metal alloys and a small amount sufficient to render said highly refined mineral lubricating oil non-corrosive to said hard metal alloys of an organic ester of selenic acid selected from the group consisting of selenic acid esters having the general formula OSe(XR.)2 and selenic acid esters having the general formula 0 TMXR) in which R is a radical selected from the group consisting of alkyl, aryl, hydroaryl, aralkyl, chloralkyl and chloraryl, Y is a halogen and X is an element selected from the group consisting of oxygen and sulfur.

9. A mineral lubricating oil non-corrosive to hard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting of cadmium-silver, cadmium-nickel and copperlead alloys which comprises a highly refined mineral lubricating oil normally corrosive to hard metal alloys and a small amount sufiicient to render said highly refined mineral lubricating oil non-corrosive to said hard metal alloys of an organic ester of selenic acid having the general formula OSe(OR)2 in which R is a radical selected from the group consisting of alkyl, aryl, hydroaryl, aralkyl, chloralkyl and chloraryl.

10. A mineral lubricating oil non-corrosive t hard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting of cadmium-silver, cadmium-nickel and copperlead alloys which comprises a highly refined lubricating oil normally corrosive to hard metal alloys and a small amount of sufllcient to render said lubricating oil non-corrosive to said hard vmetal alloy of an organic ester of selenic acid having the general formula.

0 sew R) in which R is a radical selected from the group consisting of alkyl, aryl, hydroaryl, aralkyl, chloralkyl and chloraryl and Y is a halogen.

11. A mineral lubricating oil non-corrosive to hard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting of cadmium-silver, cadmium-nickel-and copperlead alloys which comprises a highly refined lubricating oil normally corrosive ,to hard metal alloys and a small amount sufilcient to render said lubricating oil non-corrosive to said hard metal alloys of an organic ester of selenic acid having the general formula OSe(SR)z in which R is a radical selected from the group consisting of alkyl, aryl, hydroaryl, aralkyl, chloralkyl and chloraryl.

12. A mineral lubricating oil non-corrosive to hard metal alloy bearings having the corrosive .susceptibility of alloys of the group consisting of cadmium-silver, cadmium-nickel and copperlead alloys comprising a highly refined lubricating oil normally corrosive to hard metal alloys and a small amount sufiicient to render said lubricating oil non-corrosive to said hard metal alloys of an alkyl vselenate.

13. A mineral-lubricating oil non-corrosive to hard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting of cadmium-silver, cadmium-nickel and copperlead alloys comprising a highly refined lubricati'ng'oil' normally corrosive to hard metal alloys loy bearings having the corrosive susceptibility and a small amount suflicient to render said lubricating oil non-corrosive to said hard metal alloys of an aryl selenate.

14. A mineral lubricating oil non-corrosive to hard metal bearings having the corrosive susceptibility of alloys of the group consisting of cadmium-silver, cadmium-nickel and copperlead alloys which comprises a highly refined mineral lubricating oil normally corrosive to hard metal alloys and a small amount of dibutyl selenate in suilicient quantity to render said lubricating oil non-corrosive to said hard metal alloys.

15. The method of lubricating hard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting of cadmiumsilver, cadmium-nickel and copper-lead alloys in internal combustion engines which comprises applying to said bearings a mineral lubricating oil comprising a highly refined petroleum lubricating oil normally corrosive to said bearings and a small amount suflicient to render said lubricating oil non-corrosive to said hard metal alloys of an organic ester of selenic acid selected from the group consisting of selenic acid esters having the general formula OSeQIR): and selenic acid esters having the general formula in which R is a radical selected from the group consisting of alkyl, aryl, hydroaryl, aralkyl, chlor- I allwl and chloraryl. Y is a halogen, and x is an element selected from the group consisting oi oxygen and sulfur.

16. The method of lubricating hard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting of cadmiumsilver, cadmium-nickel and copper-lead alloys in internal combustion engines which comprises applying to said bearings a mineral lubricating oil comprising a highly refined petroleum lubrieating oil normally corrosive to said bearings and a small amount suflicient to render said lubricating oil non-corrosive to said hard metal alloys of an organic ester of selenic acid having the general formula OSe(OR)2 in which R is a radical selected from the group consisting of alkyl, aryl, hydroaryl, aralkyl, chloralkyl and chloraryl.

17. The method of lubricating hard metal alof alloys of the group consisting of cadmiumsilver, cadmium-nickel and copper-lead alloys in internal combustion engines which comprises applying to said bearings a mineral lubricating oil comprising a highly refined petroleum lubricating oil normally corrosive to said bearings and an organic ester of selenic acid having the general formula .lSe(0 R) in which R is a radical selected from the group consisting of alkyl, aryl, hydroaryl, aralkyl, chloralkyl and chloraryl and Y is a halogen, said organic ester of selenic acid being added in a small but sufllcient quantity to render said lubricating oil non-corrosive to said hard metal alloy.

18. The method of lubricating hard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting of cadmiumsilver, cadmium-nickel and copper-lead alloys in internal combustion engines which comprises applying to said bearings a lubricating oil comprising a highly refined petroleum lubricating oil normally corrosive to said bearings and 0.25% to 0.75% of an organic ester of selenic acid having the general formula OSe(SR)z in which R is a radical selected from the group consisting of alkyl, aryl, hydroaryl, aralkyl, chloralkyl and chloraryl.

19. The method of lubricating hard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting of cadmiumsilver, cadmium-nickel and copper-lead alloys in internal combustion engines which comprises applying to said bearings a mineral lubricating oil comprising a highly refined petroleum lubricating oil normally corrosive to said bearings and from about 0.25% to about 3% of an alkyl selenate.

20. The method of lubricating hard metal alloy bearings having the corrosive susceptibility of alloys of the group consisting of cadmiumsilver, cadmium-nickel and copper-lead alloys as described in claim 19 in which the alkyl selenate is dibutyl selenate.

CLARENCE M. LOANE. BERNARD H. SHOEMAKER.

CERTIFICATE OF CORRECTION.

?atent No. 2,160,881.

June 6, 1959.

CLARENCE n. LOAllE, ET AL.

It is-hereby certified that error'appears in the printed specification of the above numberedpatent requiring correction as follows; Page 2, second column, line 58, claim 10, strike out the word "of"; page 5, second column, line 39, claiml9, for "5%" read 2%; and that the said Letters Patent should be read with this correction therein that the seine may conform to the record of the case in the Patent Office.

Signed and sealed thisllth day of July, A.D. 1959.

(Seal) Henry Van Arsdale Acting Commissioner of Patents. 

